TW200844508A - Method for production of optical laminate, and image display device - Google Patents

Abstract

Disclosed is a method for producing an optical laminate having a coating film comprising a lyotropic liquid crystal compound, which can make the coating film approximately uniform in thickness. Specifically disclosed is a method for producing an optical laminate comprising a base material and a coating film. The method comprises the step of applying a solution containing at least one lyotropic liquid crystal compound on the base material to form a coating film, wherein the concentration of the lyotropic liquid crystal compound in the solution is lower than the (isotropic phase)-(liquid crystal phase) transition concentration. Preferably,the concentration of the lyotropic liquid crystal compound in the solution is (CIN-18) mass% to (CIN-1) mass%, wherein CIN represents the (isotropic phase)-(liquid crystal phase) transition concentration.

Description

[Technical Field] The present invention relates to a method for producing an optical layered product such as an image display device, and to the use of the optical layered body. [Prior Art 3] A liquid crystal display device is a device that uses electro-optical characteristics of liquid crystal molecules to display characters and images. At present, in a component such as a liquid crystal display device or the like, a polarizing element (also referred to as a polarizer or a polarizing film) that can extract a specific polarized light and a phase difference element that can generate a specific phase difference are also used. A retardation film, an optical compensation layer, etc.). In such a polarizing element and a phase difference element, a polarizing element and a phase difference element in which a liquid crystal compound is used as a liquid crystal compound in a liquid crystal compound is known (Patent Document) 1 and 2). Since the liquid crystal-soluble compound exhibits a liquid crystal phase in a solution state, a compound solution coated with a liquid crystal phase and coated on a suitable substrate can form a coating film of a thin film of a higher molecular film, and the coating film can be It is used in applications such as polarized diode elements and phase difference elements. [Patent Document 1] Japanese Patent Application Publication No. 2002-277636 (Patent Document 2) Japanese Patent Application Publication No. 2002-241434A SUMMARY OF THE INVENTION: J Patent Publication No. 5 200844508 However, formed from a solution of a lyotropic liquid crystalline compound The coating film is optically different in thickness and has poor light uniformity. Therefore, it is not suitable as an optical use of a polarizing element or a phase difference element, and therefore it needs to be improved. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an optical layered body which can form a thickness of the coating film substantially uniformly in an optical layered body comprising a coating film having a lyotropic liquid crystal compound. The inventors of the present invention have intensively reviewed the cause of the difference in the thickness of the conventional coating film, and have inferred that the solution is applied to the substrate without applying the solution substantially uniformly, and the present invention has been completed. The present invention relates to a method for producing an optical layered body comprising a substrate and a coating film, comprising the step of forming a coating film by coating a solution containing one or more kinds of lyotropic liquid crystal compounds on a substrate, and the solution is lyotropic The concentration of the liquid crystal compound is lower than that of the isotropic phase-liquid crystal phase. In the method for producing an optical layered body, a coating film of an oriented liquid crystalline compound can be formed by coating a solution on the substrate and drying the solution of the liquid crystal compound having a lower concentration of the phase-liquid crystal phase. The viscosity of the solution which is lower than that of the isotropic phase-liquid crystal phase is lower than that of the solution in the liquid phase state. Therefore, the above solution can be applied substantially uniformly on the substrate as compared with the conventional method. Therefore, the obtained coating film has a very small difference of 20 degrees and is suitable for use in optical applications. According to the method for producing an optical layered body of the present invention, an optical layered body excellent in thickness distribution uniformity can be obtained. Further, conventionally, a method of forming a coating film containing a solution containing a lyotropic liquid crystalline compound is prepared by applying a solution to a state in which a liquid crystal phase is displayed, and thus the solution is applied without using a liquid crystal phase solution. 6 200844508 Liquid μ丨 biochemical substance. In view of the above, the present inventors have found that a liquid crystal compound having a good orientation can be formed by using a concentration-modulated phase-to-phase phase transition phase having a low concentration (that is, a concentration of a liquid crystal phase not shown). The film obtained, and the knowledge obtained as such is the first discovery of the present inventors. 5 The invention is characterized in that the concentration of the lyotropic liquid crystalline compound of the solution is (Cw_18)% by mass to (Cin_1}% by mass, and c "is an isotropic phase-liquid crystal phase transfer concentration. Further, the present invention In another preferred embodiment, the concentration of the lyotropic liquid crystalline compound of the solution is from 1% by mass to 18% by mass. 1〇X 'The other preferred manufacturing method of the present invention is the refractive index ellipsoid of the coating film showing nx Further, in the other preferred embodiment of the present invention, the substrate comprises a polymer film or a laminate comprising a polymer film and an oriented film. Further, the other preferred manufacturing method of the present invention. The method is characterized in that the alignment film is a polycyclic compound having two or more aromatic rings and/or a heterocyclic ring, and the present invention is a polycyclic compound having two or more aromatic rings and/or a hetero ring. Another preferred embodiment of the method of manufacture is that the molecular structure of the lyo liquid compound has _8〇3馗 and/or _(showing relative ions). COOM (and further, other preferred forms of the invention) Manufacture of the sample ^^ ⑴ represented by the following formula containing many cyclic compound: [Chemical 1] 7200844508

In the formula (I), Μ represents a relative ion, and k, 1, m, and η represent the number of substitutions (k and 1 are integers of 0 to 4, and m and η are integers of 0 to 6), but k, 1, When m and η are not different, they are 0. Further, the present invention provides an image display apparatus having an optical layered body obtained by any of the above manufacturing methods. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a layer structure of an optical layered body of the present invention.

C Embodiment: J 10 BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an optical layered body of the present invention comprises coating a substrate with a solution having a concentration of a lyotropic liquid crystalline compound having a lower concentration of an isotropic phase-liquid crystal phase. The film step, and by drying the coating film, a coating film having a uniform thickness can be formed. 15 Hereinafter, the present invention will be specifically described. <Optical laminate of the present invention> The optical layered body obtained by the production method of the present invention has a substrate and a coating film containing a lyotropic compound. As shown in Fig. 1(a), the optical laminate may be a laminate of two layers composed of the substrate 2 and the coating film 38 200844508, or may be as shown in Fig. 1(b). The material 2 and the outer surface of the coating film 3 further contain three or more layer layers of the other layer 4! For example, a retardation film, a polarizing element, an adhesive layer or the like can be used as the other layer 4. (Substrate) 5 10 15 The above-mentioned substrate is used for uniformly developing a liquid containing a lyotropic liquid crystalline compound, and the substrate is not particularly limited as long as it can be uniformly formed, and for example, a synthetic resin film can be used. The film is generally referred to as a sheet, a glass plate or the like. In a preferred embodiment, the substrate is a separate polymeric film, and in other preferred embodiments, the substrate comprises a laminate of a permanent film. Further, the laminate containing the polymer film preferably contains an oriented film in the polymer film. The phantom film is not particularly limited, and is preferably thin with excellent transparency (for example, a haze value of 5% or less). The polymer film may, for example, be a polyester system such as polyethylene terephthalate or monomethyl phthalate; a cellulose system such as diethyl phthalocyanine or triacetyl cellulose; Carbonate type; propylene type such as poly(methyl methacrylate); styrene type such as polyphenyl nitrile styrene copolymer; polyethylene, polypropylene, hydrazine, hydrazine or norbornene (n〇rb〇) Rnene) structure of polyene, ethylene propylene copolymerization &, system, chloroacetin, amide, aromatic amine and other amides; imine and other quinone imine; polyether oxime; polyether ether a ketone system; a polyphenylene sulfide system; an acetol alcohol group, a cockroach, a bismuth, a diethylene vinylene; an ethylene butyraldehyde system; an acrylate system; a polycondensation; a polymer film such as an epoxy resin; These two or more kinds of mixtures are included: + ruthenium film, etc. The polymer film can also be used as a laminate of two or more kinds of polymers. 20 200844508 These polymer films are preferably made using an extended film. The thickness of the substrate can be appropriately designed depending on the strength, etc., but it is preferably 3 Å//m or less, and more preferably from the viewpoint of general thinness and light weight. It is 5~fine, and the best one is 1〇~1〇〇//111. 5 The right side 4 substrate contains an oriented film, and the oriented film is preferably subjected to orientation treatment. The above-mentioned orientation treatment may, for example, Mechanical orientation treatment such as rubbing treatment, chemical orientation treatment, etc. The mechanical orientation treatment can be performed by one side of the substrate (or one of the suitable coating films formed on one side of the substrate), and the cloth is equal to one The film may be formed on one side of the substrate. Alternatively, an extension film subjected to the stretching treatment may be used. The film or the coating film subjected to the rubbing treatment or the stretching treatment is not particularly limited. A polymer film or the like exemplified as the film for a substrate is used, and from the viewpoint of the alignment efficiency of the liquid crystal compound, the alignment film is preferably a quinone-based polymer. 15 Chemical directional treatment can be performed by a substrate Forming a light directing film 'containing a directing agent on one side and irradiating the light directing film with light. Thereby, an oriented film can be formed on one side of the substrate. The directing agent can, for example, have a photoreaction which produces a photochemical reaction. A functional group-based polymer or the like, and the photochemical reaction is a photoisomerization reaction, a photo-clearing ring-closing reaction, a photodimerization reaction, a photodecomposition reaction, and an optical Fries rearrangement. The photo-alignment film can be formed by dissolving a directing agent in a solvent in a suitable solvent and applying it to a substrate. (> Valley-liquid crystalline compound) The lyotropic liquid crystal used in the present invention The compound can be used as long as it can be coated with 200844508 on a substrate and dried to form a coating film. It is not a liquid crystal compound, and it can be used as a phase difference element. 'The ring is better' ^ The heterocyclic ring is more preferably a nitrogen atom. Further, the lyotropic liquid crystalline compound has a molecular structure or a _c(x)M (and m and the following formula ( I) the same) is better. It is preferable to use a polycyclic compound as the liquid crystal compound. The compound has an aromatic or more aromatic ring and/or a heterocyclic ring, and preferably has 4 to 8 aromatic: rings and/or heterocycles. Further, the basic skeleton of the polycyclic compound has at least 10 (a lyotropic liquid crystalline compound which forms a phase difference element). If the lyotropic liquid crystalline compound can form a phase difference element, the lyotropic liquid crystalline compound It is preferred that the molecular structure contains a quinoxaline derivative unit. The lyotropic liquid crystalline compound is more preferably a derivative unit of acenaphtho [l, 2-b] quinoxaline 15 in a molecular structure. Most preferred is a lyotropic liquid crystalline compound containing a fluorenyl [u-b] porphyrin derivative unit having at least one of -SCbM and -COOM. The porphyrin derivative is exemplified by the fluorenyl [l, 2-b] quinoxaline derivative represented by the following formula (1). In the formula (I), k and 1 are independent integers of 44 to 20, respectively, and m and η are independent integers of 66, respectively, and Μ represents relative ions, but when k, 1, m, and η are different It is preferred that the foregoing hydrazine is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, a metal ion, and a substituted or unsubstituted ammonium ion. Metal ions can be exemplified by, for example, Ni2+, Fe3+, Cu2+, Ag+, Zn2+, Al3+, Pd2+, Cd2+, Sn2+, 11 200844508

Co2+, Mn2+, Ce3+, and the like. [Chemical 2]

As shown in the following formula (a), the aforementioned dangerous [l, 2-b] eucalyptus derivative may be, for example, a hydrazinium [l,2-b] porphyrin or a carboxylic acid thereof, The fumes 5 sulfuric acid, or the chlorine acid are obtained by acidification. In the formula (a), k, 1, m, η and Μ are the same as those of the formula (I) (however, when k and η are not different, they are 0). [化3]

Further, as shown in the following formula (b), the anthra[1,2-b] porphyrin derivative may be, for example, a sulfonic acid group and/or a carboxyl group of benzene-1,2-diamine. The derivative, 10 is obtained by a condensation reaction with an acid group and/or a Wei group derivative of acenaphthoquinone. In the formula (b), k, 1, m, η and lanthanum are the same as in the formula (I) (however, k, 1, m and η are different when they are 0). [化4] 12 200844508 (M03sv (M〇3S)k (COOM),

(MOOC)m (S〇3M)n (COOM)丨

(S〇3M)i (MOOC), the aforementioned anthracene [l,2-b] porphyrin derivative is shown in a liquid crystal phase (i.e., lyotropic liquid crystal) in a solution state of a predetermined concentration. Further, the liquid crystal phase is preferably a nematic liquid crystal phase from the viewpoint of excellent orientation. The nematic liquid crystal phase also includes a person who forms a supramolecule and exhibits a nematic state in the formed body. A phase difference element can be produced by forming a film of a solution containing the above-mentioned indeno[l,2-b]porphyrin derivative. The above-mentioned indeno[l,2-b]porphyrin derivative can be used to produce a transparent phase difference element having a high in-plane birefringence and having no absorption or absorption in the visible light region. The phase difference element obtained by forming the above solution is formed by coating, so that a thin thickness can be formed. Further, the refractive index ellipsoid of the phase difference element of the present invention satisfies the relationship of nx - nz > ny (nx > nz > ny or nx = nz > ny), and displays the birefringence in the high plane. Therefore, the phase difference element of the present invention can have a particularly thin thickness compared to the conventional phase difference element, and an ideal phase difference value can be obtained. In addition, in the present specification, "nx = nz" does not mean that nx and nz are completely the same, and substantially the same. Further, when nx and nz are substantially the same, for example, Rth[590] is -10 nm to 10 nm, and preferably -5 nm to 5 nm. Here, in the present specification, "nx" and "ny" respectively indicate the refractive index in the in-plane orthogonal direction (however, nxgny), and "nz" indicates the refractive index in the vertical direction with respect to the face of 13 200844508. The transmittance of the retardation element at a wavelength of 590 nm is preferably 85% or more, and more preferably 90% or more. The thickness of the phase difference element is preferably 0 〇5//m 〜5 //111, and more preferably 〇.1//111 〜5//111. 5 The birefringence (Δ nxy[590]=nx-ny) of the phase difference element in the plane at a wavelength of 590 nm is preferably 0.01 or more, and more preferably 〇.5 or more, and 0.1 to 0.5. . Further, the above ^1^/590] can be suitably adjusted in the above range by the molecular structure of the polycyclic compound. Further, the phase difference element has a phase difference value 10 (Re[590]) in the plane of the wavelength of 590 nm, and an appropriate value can be set according to the purpose. This Re[59〇] is preferably 10 nm or more and preferably 20 nm to 300 nm. In addition, the in-plane phase difference Re[ λ ] is the phase difference in the plane in the wavelength (nm) at 23 ° C. ReU] can be obtained by setting Re [A] = (nx_ny) xd when the thickness is set to d (nm). Rth[590] of the phase difference element can be obtained by setting an appropriate value within a range in which the refractive index ellipsoid satisfies the relationship of nx 15 -nz > ny. The difference between the phase difference (Re[59〇]) of the phase difference element in the plane of the wavelength of 590 nm and the phase difference (Rth[590]) in the thickness direction (Re[590]-Rth[590]) l 〇 nm 〜 2 〇〇 nm is better, and is preferably 2 〇 nm 〜 2 〇〇 mn. Further, the phase difference Rth [A] in the thickness direction is the phase difference of the thickness in the wavelength λ (ηηι) at 23 °C. Rth[;l] can be obtained by setting Rth[ λ ]=(nx_nz)xd when the phase thickness is d (nm). The Nz coefficient of the phase difference element is preferably -0.11 to 0.9, and is preferably 0 to 0.9' and 0.1 to 0.7. The phase difference element whose coefficient is within the above range can be utilized for optical compensation of liquid crystal cells of various driving modes. In addition, 14 200844508

The Nz coefficient is a value calculated by Rth[59〇]/Re[590]. Further, the retardation value (D) of the phase difference element is preferably 1 〇 5 or more, and more preferably 1.06 to 1.15. Further, the wavelength dispersion value (D) is a value calculated by the formula: D = Re [480] / Re [550]. 5 (a lyotropic liquid crystal compound forming a polarizing element) The lyotropic liquid crystalline compound contains an azo derivative unit and a vermiculite in its molecular structure, if the lyotropic liquid crystalline compound can form a material of the polarizing element. Derivative units, anthracene derivative units, indanthrene derivative units, and/or imidazole derivative units are preferred. Further, the lyotropic liquid crystalline compound which forms the polarizing element is preferably a chromotropic dye which exhibits liquid crystallinity represented by the following formula (1). Formula (1): (pigment) (S03M) n (and M shows a cation). The enthalpy of the formula (1) is preferably a metal ion such as a hydrogen ion, Li, Na, K or Cs, an ammonium ion or the like. 5 If the 'pigmentary part is a unit containing an azo derivative unit, a derivative derivative unit, a derivative unit, an indanthrene derivative unit, and/or a sodium salivation unit. In the case of the dichroic dye represented by the formula (1), the azo compound such as the azo compound in the solution will become a hydrophobic portion, and the acid 20 and its salt will become hydrophilic sites. By the balance of the two, the mixture between the hydrophobic sites and the hydrophilic (four) sites is found to be the lyotropic liquid crystal phase. Specific examples of the dichroic dyes represented by the formula (1) are as follows. The compounds represented by the following general formulae (2) to (8), etc. [Chemical 5] 15 200844508

ArNH or (2)

ArCOKH 〇 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group and an ethyl group. The aryl group (Ar) is preferably a substituted or unsubstituted phenyl group, and it is more preferred to substitute the phenyl group at the 4-position with no substitution or chlorine. Further, hydrazine is the same as the above formula (1) 5 . [6] 16 200844508

(A) (B) In the formulae (3) to (5), A is represented by the formula (A) or (B), and η is 2 or 3. R3 of the formula (Β) shows hydrogen, an alkyl group, a halogen or an alkoxy group, and Ar of the formula (Α) shows a substituted or unsubstituted aryl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and the halogen is preferably bromine or chlorine. Further, the alkoxy group is preferably an alkoxy group having 1 or 2 carbon atoms, and more preferably a methoxy group. The aryl group is preferably a substituted or unsubstituted phenyl group, and a phenyl group which is unsubstituted or substituted with a methoxy group, an ethoxy group, a chlorine group or a butyl group or a methyl group at the 3-position is preferred. The hydrazine is the same as the above formula (1). 17 200844508 【化7】

In the formula (6), η is an integer of 3 to 5, and Μ is the same as the above formula (1). 【化8】 Ο Η

Η 〇 (S〇3M) 2 Formula (7) In the formula (7), hydrazine is the same as the above formula (1). 5 [Chemical 9] 〇00=00 • (so3M)2 Formula (8) In the formula (8), Μ is the same as the above formula (1) 18 200844508 A borrowing month) 3 solution of a liquid crystal compound The film can be made into a light-emitting element, and a polarizing element having high luminosity can be produced by using an arrow, a +, and a smattering liquid crystal compound. The polarizing element obtained by the β ^ film-forming solution is thinned by coating 5 . The polarizing element obtained has a degree of polarization of preferably 99% or more, more preferably 99.5% or more. Further, the single-transmittance of the polarizing element is preferably 仞% or more, and the content is preferably 42% or more. &lt;Manufacturing Method of Optical Laminate of the Present Invention&gt; 10 The method for producing an optical layered body of the present invention preferably has the following steps A to C 〇' Step A: applying a solution containing one or more kinds of lyotropic liquid crystalline compounds to a substrate The step of forming a coating film. Step B · Dry the aforementioned coating film step. 15 Step C · The surface of the dried coating film in the above step B is contacted with a compound liquid containing a salt of a compound selected from the group consisting of aluminum salts, barium salts, lead salts, chromium salts, barium salts, and intramolecular inclusions. At least one of the group consisting of two or more compound salts of an amine group. The substrate may also be subjected to a directional treatment on the side of the coating solution. In addition, hereinafter, the solution containing the lyotropic liquid crystalline compound of the present invention is referred to as a "coating solution", and the coating film formed by applying the coating solution is referred to as a "wet coating film", and the wet coating film is dried. The coating film in the state is "dry (Step A) 19 200844508. Step A is a step of applying a solution containing a lyotropic liquid crystalline compound to the substrate and forming a wet coating film on the substrate. The substrate can be used as described above. The solution containing the lyotropic liquid crystalline compound used in the step A contains 5 solvents and one or more of the above lyotropic liquid crystalline compounds, and the solvent is preferably water-containing. The lyotropic liquid crystalline compound may be exemplified by the foregoing. If appropriate, one or two or more kinds may be used alone. The concentration of the lyotropic liquid crystalline compound in the coating solution may be adjusted to a concentration lower than that of the isotropic phase-liquid crystal phase, and the concentration coating solution is not shown. The concentration of the liquid crystal phase. The isotropic phase-liquid crystal phase transfer concentration can be confirmed by the light pattern of the solution observed by a polarizing microscope. The concentration of the lyotropic liquid crystal compound of the coating solution is (CIN) _丨8) mass% ~ (CIN-1) mass% is better, more preferably (c "丨0) mass% ~ (Qn_2) mass 15%, and where Cin represents isotropic phase-liquid crystal phase transfer Specifically, the concentration of the lyotropic liquid crystalline compound of the coating solution is preferably 质量 by mass% to 18% by mass, more preferably 丨% by mass to 18% by mass, and most preferably 5% by mass to 18% by mass. Further, the viscosity of the coating solution is preferably 〇·s 30 mPa · s, more preferably 〇·5ιηΡα · s~3mpa · s, and the viscosity system 20 is a rheometer (made by Haake Co., Ltd.). Product name: 600, measurement conditions: the value measured by the double cone sensor (d〇uble (7) still sinking rate 1000 (l/s)]. Since the coating solution of the present invention is used at a lower concentration, It has excellent solution fluidity, and can also be easily prepared in the coating viscosity range of the coating machine (for example, applicator, etc.). Therefore, it is used to form a uniform coating. Water as a solvent for the coating solution, the conductivity of water is preferably s / cm or less (lower limit 値〇 &quot; s / cm), preferably For the coffee heart (10) ~ 5 / cm, the best one is 〇. 〇 1 / / coffee ~ 5 to -. By using the solution of water conductivity inside, can form a coating film with excellent uniformity. The conductivity can be determined by using the solution conductivity (Electronics Fines Co., Ltd.), product name: CM_11TJ. In addition, the coating solution may contain any solvent as appropriate, in addition to water as a solvent. For example, alcohols, lysines, succulents, ketones, sucrose, etc., and these solute can be used alone or in combination of two or more. Further, the coating solution is preferably adjusted to have a pH of about 10 to 10, and About ρΗ6~8 is better. 15 Materials 'Additives may also be added to the aforementioned coating solution. The additive may, for example, be a plasticizer, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, a device, a toner, an antistatic agent, a compatibilizer. , parental agents, and thickeners are stupid. Look for the addition amount of 4 special additives, which is more than 0 Berry / 〇. Further, a surfactant which is added as 20 agents may be added to the coating solution, and the surfactant is used to enhance the concentration and coatability of the polycyclic compound on the surface of the soil. The surfactant preferably has a nonionic interface activity of more than 0 and 5% by mass or less. The amount of the surfactant added is preferably. The method of applying a coating solution to the surface of the substrate may be, for example, a coating method of 21 200844508 using a suitable applicator. The applicator may be, for example, a reverse roll coater, a positive roll coater, a gravure coater, a rod coater d coater, a slit die coater (sl〇t die (7) age), a slit orifice type Slot orifice coater, curtain coater (four) like c〇ater), spray coater (fountain coater) and the like. (Step B) Step B is a step of drying the coating film applied on the substrate. The aforementioned wet coating film is dried by a suitable and appropriate method. The drying method can be exemplified by an air circulating type strange temperature furnace which is hot air or cold air, a heating means which is heated by microwave or far infrared ray, a temperature which is heated to adjust the temperature, a heat pipe, or a metal belt. The drying temperature is below the isotropic phase transition temperature of the solution, and it is preferred to gradually increase from a low temperature L to dry. The aforementioned drying temperature is 1 Torr. 〇~8〇 It is better, and more U is 20 C~60 C. If it is within such a temperature range, a dry coating film having a small difference of 15 degrees can be obtained. The drying time can be appropriately selected depending on the drying temperature and the type of the solvent, and in order to apply a dry coating film having a small difference in thickness, the drying time is, for example, i minutes to minutes, and preferably 1 minute to 1 minute. In the case where the edge coating film is dried during the drying process, the liquefied liquid is directionally dissolved and the lyotropic liquid crystal compound is fixed in this state. The thickness of the obtained dry (four) is preferably 0.05_~10//m, more preferably: β 5 (four). The amount of the solvent remaining in the dried coating film is preferably 1% by mass or less, more preferably 0.5% by mass or less. (Step C) 22 200844508 Step c is a step of imparting water resistance to the surface of the dried coating film (joining surface and opposing surface of the substrate). Specifically, the surface of the dried coating film formed in the above step B is contacted with a solution containing a salt of a compound selected from the group consisting of a salt of a salt, a salt of a cerium, a salt of a cerium, a cerium salt, a cerium salt, and a molecule. At least one of the group consisting of a compound salt containing two or more amine groups. The above compound salt may, for example, be aluminum chloride, barium chloride, lead chloride, chromium sulfide, barium chloride or 4,4'-tetramethyldiaminodiphenylmethane hydrochloride. &gt; 1〇2,2 - - 2,2,- dipyridyl hydrochloride, 4,4,_ σ ratio dimethylamine hydrochloride, melamine hydrochloride, tetraamine Pyrimidine hydrochloride (she knows well-hydrochloride - hydrochloride) and so on. By forming a layer of such a compound salt, the surface of the dried coating film can be made insoluble or insoluble to water. Therefore, water resistance can be imparted. The concentration of the compound salt in the solution containing the salt of the above compound is from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass. When the surface of the dried coating film is brought into contact with the solution containing the salt of the above compound, for example, a method of applying a liquid containing the compound salt to the surface of the coating film, and immersing the coating film in a salt containing the compound salt may be employed. Any method such as the method of 20 liquids. If such a method is employed, the surface of the dried coating film is preferably washed with water or any solvent and dried. <Uses of Optical Laminates> The use of the optical laminate of the present invention is not particularly limited, and examples thereof include a λ / 4 plate of a liquid crystal display device, a Λ /2 plate, and a viewing angle expansion 23 200844508 large film. , polarizing film, etc. to! In the embodiment, the optical product of the present invention may be laminated with a polarizing element as a polarizing plate using a phase difference element polarizing plate. , indicating that the 5 _ partial wire, at least need to have the hair (four) pieces. The eccentricity may also contain other filaments, polarizers or any other material. From the point of view of reality, an appropriate layer can be arbitrarily set between the layers of the member and the member. The polarizing member of the light plate can be used to transfer natural light or polarized light to each layer. ) Polarized person. Preferably, the polarizing element is formed by using a moth or a binary resin of 2 as a linear resin, and a hanging film of 5/zm to 50/m. dry. The amount of the sub-layer 15 20 can be used as long as it can adhere to the surface of the adjacent member and can be sufficiently bonded to the bonding force during the bonding time. Shaped wire materials for the financial sector = choose the right person to take the agent, adhesive, heart layer agent (coffee hor _ agent). The surface of the adhesive layer (4) forms a bonding layer layer, and a multilayer structure of an adhesive layer=layer is formed thereon, and a thin layer (also referred to as a hairline (10) which is unrecognizable to the naked eye is disposed on the side of the optical layered body. The layer may be the same as or different from the layer disposed on the other side. In the case of the optical layering system of the present invention, the polarizing element is used as a polarizing plate, and in the polarizing plate, β may be used. Other silk bodies, protective layers of other retardation elements, etc. 4彳Μ 24 200844508 The use of the optical laminate obtained by the production method of the present invention is not particularly limited, and the optical laminate can be preferably used as an image display device. The image display device of the present invention comprises a liquid crystal display device, an organic EL display device, a plasma display device, and the like, and the preferred use thereof is a television (in particular, a large TV having a screen size of 40 inches or more). The image display device is a liquid crystal display device, and the preferred uses thereof are: a personal computer screen, a notebook computer, a photocopying machine, and the like; a mobile phone, a clock, a digital camera, and an individual. Portable devices such as digital assistants (PDAs) and portable game consoles; electrical equipment for homes such as cameras and microwave ovens; reversing monitors, monitors for car navigation systems, car audio, etc.; The present invention is further described with reference to the embodiment and the comparative example. The present invention is not limited to the following embodiments. In addition, each analysis method used in the Example is as follows. (1) Method for measuring nx, ny, nz, and Re[590], Rth[590], and Nz coefficient: Using the prince measuring machine (company) The product name 20 "KOBRA21-ADH" was measured at 23 ° C. The average refractive index was measured using an Abbe refractometer [ATAGO Co., Ltd., product name "DR-M4"]. (2) Measurement method of single transmittance and polarization degree: Using a spectrophotometer [Muragami Color Technology Research Institute Co., Ltd. 25 200844508, product name "D〇T-3"], at 23° Article C In addition, the measured values of the degree of polarization and the transmittance of the single body are based on the wavelength of 55 〇 mn. The single transmittance is based on the value of the tristimulus value of the 2 degree field of view of JIS Ζ 8701-1995. By measuring the parallel transmittance (Η.) and the orthogonal transmittance (Η90), and obtaining the polarization degree ^{(ΗγΗΜ/^+Η^^χΙΟΟ. Parallel transmittance (H.) is a parallel type laminated body. The value of the transmittance, and the parallel type laminated system makes the optical laminated bodies of the two measuring objects parallel to each other and has a weight of $. The straight parent transmittance (H%) is the transmittance of the orthogonal laminated body. The 10-valued L-direct straight-type laminated system makes the absorption axes of the optical laminates of the two measurement objects overlap each other orthogonally to produce &amp; In addition, these transmittances are based on the 2-degree field of view (C light source) of Cong, and the gamma value of the luminosity correction is performed. (3) Measurement of thickness and thickness difference · The thickness of the sample was measured using a touch-type surface shape measuring device 15 [DEKTAK] manufactured by ULVAC, and the thickness was measured by wiping the coated film with a water-containing waste fabric. Part of it is just the difference. The difference in thickness is from the in-plane (l2cmxl2cm) of the sample, and arbitrarily selects 3 places in the longitudinal direction and 3 places in the lateral direction (the interval between each point is 3cm), and the difference between the maximum value and the minimum value is used as the thickness difference. . 20 [Synthesis Example 1] &lt; Synthesis of 苊[l,2-b] 噚噚琳&gt; In a reaction vessel equipped with a blender, glacial acetic acid 5 L and refined B-baked naphthalene were added to 490 g, and After the nitrogen bubble, the sandalwood fell for 15 minutes, and the B ruled into the brewing solution. Similarly, in a separate vessel with a transfer machine, 7.5 L of acetic acid and 275 g of o-p-diamine were added, and stirred under nitrogen bubbles for 15 minutes to obtain an o-phenylenediamine solution. Thereafter, the o-phenylenediamine solution was gradually added to the ethanenaphthylquinone solution in a nitrogen atmosphere under stirring for 1 hour, and then stirred for 3 hours to cause a reaction. After adding ion exchange to the obtained reaction liquid, the precipitate was filtered to obtain a crude product. The crude product was recrystallized by hot glacial acetic acid. [Synthesis Example 2] <Synthesis of l[l,2-bp quinone+lin-2,5-disulfonic acid> As shown in the following reaction scheme, the oxime obtained according to the synthesis example is [^7] 10喳300 g of porphyrin was added thereto with 30% fuming hydrochloric acid (2.1 L) and stirred at room temperature for 24 hours, then heated to 130 and stirred for 32 hours to cause a reaction. While maintaining the obtained solution, it was diluted with 4 (TC~5 (TC) by adding 4.5 L of ion-exchanged water, and stirred for further 3 hours. The precipitate was filtered and recrystallized with sulfuric acid to obtain the enthalpy of the following formula (4) and [l, 2-b] porphyrin_2,5_disulfonic acid. 15 5 ion exchange water muscle (conductivity: G.M (four) dissolved in the reaction, and then added with aqueous sodium hydroxide solution. Add the obtained aqueous solution to supply The high-pressure muscle test of the reverse osmosis membrane filter [product name wm] manufactured by Nitto Denko Yushoku Co., Ltd. is added to the tank, and the reverse osmosis water is added to make the liquid amount constant and the circulation is filtered. The residual conductivity of sulfuric acid is removed until the conductivity of the waste liquid is W3.6 &quot;s/cm. 27 200844508 [Chem. 10]

S〇3H Na03S

NaOH

S03Na (C) &lt;Synthesis of [l,2-b]porphyrin-2-sulfonic acid&gt; As shown in the following reaction scheme, the oxime [1,2-b] obtained according to Synthesis Example 1 was obtained. 5 porphyrin 300 g, 30% of fuming hydrochloric acid (2.1 L) was added thereto, and stirred at room temperature for 48 hours to cause a reaction. While maintaining the obtained solution at 40 ° C to 50 ° C, it was diluted with 4.5 L of ion-exchanged water, and stirred for further 3 hours. The precipitate was filtered to obtain hydrazine [l,2-b]porphyrin-2-sulfonic acid represented by the following formula (d). The reaction product was dissolved in ion-exchanged water 30 L (conductivity: 0.1//S/cm), and neutralized by adding an aqueous sodium hydroxide solution. The obtained aqueous solution was added to a supply tank, and a high-pressure RO element test apparatus having a reverse osmosis membrane filter [product name "NTR-7430 filter element" manufactured by Nitto Denko Corporation) was used, and a reverse osmosis water was added thereto to increase the amount of liquid. The filtration was carried out while being constant, and the residual sulfuric acid was removed until the conductivity of the waste liquid was 8.1//S/cm. 15 【化11】

30% oleum

NaOH

S〇3H

S〇3Na (d) 28 200844508 [Reference example] <苊,[1,2-b]porphyrin-2,5-disulfonic acid and indeno[1,2-b]喧$ σ林-2 - Preparation of aqueous solution of a mixture of sulfonic acids&gt; The aqueous solution obtained in the above Synthesis Example 2 and Synthesis Example 3 was mixed to give the above-mentioned 5 synthetic Example 2 the erbium [1,2-b] Ditergent acid, and the solid content of the dangerous [1,2-b] sigma lindane__hemeic acid, which was paid in the above-mentioned Example 3, was 65 mass parts: 35 parts by mass. . Next, the coating bath was prepared using a rotary evaporator so that the concentration of the above-mentioned skeletal compound (two kinds of people) in the aqueous solution was 25% by mass. Here, the solution was observed with a polarizing microscope, and 10 showed a nematic liquid crystal phase at 23 °C. [Examples] Acrylic glass (manufactured by Songlang Glass Industry Co., Ltd., vertical X transverse: 45 mm x 50 mm, thickness 0.7 mm) was washed with an ultrasonic cleaner. This ultrasonic cleaning was initially carried out in acetone for 3 minutes and then in ion-exchanged water 15 for 5 minutes. By coating the surface of the acrylic glass after the cleaning, spin coating was used to coat the brewed imine, and dried and fired to form an oriented film. The coating conditions were initially 10 〇〇Γ η 5 5 seconds, followed by 3 〇〇〇 rpin for 20 seconds, and the firing conditions were initially at 120 ° C for 30 minutes and then at 28 (TC for 60 minutes. The rubbing cloth wipes the surface of the oriented film 5 times in one direction, and performs rubbing treatment. Then, the corona discharge treatment is performed on the surface of the rubbed acrylic glass by a corona treatment machine. Corona treatment condition is speed 3111 / min, output 〇.14kW, discharge amount 155.6W min / m2. Then 'add ion exchange water to the aqueous solution obtained from the above reference example to prepare the coating solution, so that the concentration of the lyotropic liquid crystal compound becomes 15 29 200844508 The mass ratio of the aqueous solution to the isotropic phase liquid crystal phase is 35 mass% at 35 ° C, and the liquid crystal phase is not displayed in 15 mass%. The coating bar is used in a constant temperature room at 23 ° C (manufactured by BUSCHMAN) The name "mayerrotHSl.5") is coated on the oriented film to a thickness of 4.1/zm, 5 to be naturally dried. The dried coating film thus obtained is a phase difference element, and its refractive index ellipsoid shows nx &gt; nz &gt; The relationship of ny. The thickness of the dry coating film is 620 nm, and the difference in thickness is ±50 nm. 10 Further, the monomer transmittance at the coating film wavelength of 59 〇 nm is 95.6%, and the in-plane retardation value in the wavelength 590 nm (Re[590] The system 203.6 has a thickness direction phase difference (Rth[590]) at a wavelength of 590 nm of 53.2 and an Nz coefficient (Rth[590]/Re[590]) = 0.25. [Comparative Example] 15 Except for direct use of Reference Example 1 A solution prepared by using a medium (i.e., a concentration of a lyotropic liquid crystal compound of 25% by mass) was used as a coating solution, and a coating film was produced in the same manner as in the examples. The obtained coating film thickness was 62 〇 nm. The difference in thickness is ±15 〇 nm. [Simple description of the drawings 3 20 Fig. 1 is a cross-sectional view showing an example of the layer structure of the optical layered body of the present invention. [Explanation of main component symbols] 1···Laminated body 3··· Coating film 2...substrate 4...other layer 30

Claims (1)

200844508 X. Patent Application Range: 1. A method for producing an optical laminate, which is a method for producing an optical composite layer of a substrate and a coating film, comprising coating a solution containing one or more lyotropic liquid crystal compounds on a substrate. Forming a coating process, 5 and the concentration of the lyotropic liquid crystalline compound of the solution is lower than that of the isotropic phase-liquid crystal phase. 2. The method for producing an optical laminate according to the first aspect of the invention, wherein the concentration of the lyotropic liquid crystalline compound of the solution is (CIN-18)% by mass to (Cin-1)% by mass and the Cin table is different. The concentration is transferred to the phase-liquid crystal phase. The method for producing an optical layered body according to the first aspect of the invention, wherein the concentration of the lyotropic liquid crystalline compound of the solution is from 1% by mass to 18% by mass. 4. The method of producing an optical laminate according to the first aspect of the invention, wherein the refractive index ellipsoid of the coating film exhibits a relationship of nx$ nz &gt; ny. The method of producing an optical layered body according to the first aspect of the invention, wherein the substrate is a polymer film or a laminate comprising a polymer film and an alignment film. 6. The method of producing an optical layered body according to claim 5, wherein the oriented film is a polyimide. The method for producing an optical layered product according to the first aspect of the invention, wherein the lyotropic liquid crystalline compound is a polycyclic compound having two or more aromatic rings and/or heterocycles. 8. The method of producing an optical layered body according to claim 1, wherein the lyotropic liquid crystalline compound has -S03M and/or 31 200844508 -COOM in a molecular structure, and Μ represents a relative ion. 9. The method for producing an optical layered body according to the first aspect of the invention, wherein the lyotropic liquid crystalline compound contains a polycyclic compound represented by the following formula (I): (MOOC)m (S〇3M)n In the formula (I), Μ represents a relative ion, and k, 1, m, and η represent a substitution number (k and 1 are integers of 0 to 4, m and η are 0 to 6) Integer), however, k, 1, m, and η are not 0 at the same time. 10. The method of producing an optical laminate according to claim 1, wherein the solution contains water. An image display apparatus comprising the optical layered body obtained by the method of manufacturing the first aspect of the patent application. 32